JP4775908B2 - Olefin polymerization catalyst and process for producing olefin polymer using the same - Google Patents

Description

  The present invention is capable of maintaining a high degree of stereoregularity and yield of a polymer, and has a great effect on the melt flow rate of hydrogen content, that is, a catalyst for polymerization of olefins having a good hydrogen response and the olefins using the same. The present invention relates to a method for producing a polymer.

Conventionally, in the polymerization of olefins such as propylene, solid catalyst components containing magnesium, titanium, an electron donating compound and halogen as essential components are known. Many methods for polymerizing or copolymerizing olefins in the presence of an olefin polymerization catalyst comprising the solid catalyst component, an organoaluminum compound and an organosilicon compound have been proposed. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 57-63310) and Patent Document 2 (Japanese Patent Laid-Open No. 57-63311), a solid catalyst component containing a magnesium compound, a titanium compound and an electron donor, and organic There has been proposed a method for polymerizing olefins having 3 or more carbon atoms in particular using a catalyst comprising a combination of an aluminum compound and an organosilicon compound having a Si—O—C bond. However, these methods are not always satisfactory for obtaining a high stereoregularity polymer in a high yield, and further improvement has been desired.
Moreover, in patent document 3 (Unexamined-Japanese-Patent No. 1-315406), titanium tetrachloride is made to contact the suspension formed with diethoxymagnesium and alkylbenzene, and it is made to react by adding phthalic acid dichloride next. Propylene polymerization catalyst comprising a solid catalyst component prepared by obtaining a solid product and further catalytically reacting the solid product with titanium tetrachloride in the presence of an alkylbenzene, and an organoaluminum compound and an organosilicon compound, and the catalyst Propylene polymerization methods in the presence of are proposed.
Each of the above prior arts has such a high activity that the purpose of removing a catalyst residue such as chlorine and titanium remaining in the produced polymer can be omitted, and at the same time, a stereoregular polymer. Although efforts have been made to improve the yield and to increase the sustainability of the catalyst activity during the polymerization, each of them has achieved results, but improvement of the catalyst for such purpose is still desired.
By the way, the polymer obtained by using the catalyst as described above is used for various uses such as containers and films in addition to molded articles such as automobiles and home appliances. These melt the polymer powder produced by polymerization and are molded by various molding machines. Especially when producing large molded products by injection molding, the fluidity of the molten polymer (melt flow rate, MFR) The olefin-based thermoplastic elastomer (hereinafter referred to as “TPO”) is preferably used in the copolymerization reactor in order to reduce the cost of the highly functional block copolymer for automobile materials. A method for producing TPO in a polymerization reactor directly without adding a newly synthesized copolymer after production and producing as many copolymers as necessary for production, that is, reactor-made by direct weight as referred to in the industry In the production of TPO, the melt flow rate in the homopolymerization stage is used to keep the melt flow rate of the final product sufficiently large and facilitate injection molding. Is may be required more than 200 values, many studies have been made to increase the melt flow rate of the order polymer.
The melt flow rate is highly dependent on the molecular weight of the polymer. In the industry, it is a common practice to add hydrogen as a molecular weight regulator for the polymer produced in the polymerization of propylene. At this time, in order to produce a low molecular weight polymer, that is, in order to produce a polymer having a high melt flow rate, usually a large amount of hydrogen is added. However, in a bulk polymerization apparatus, the pressure resistance of a reactor is particularly limited due to its safety. There is also a limit to the amount of hydrogen that can be added. Further, even in the gas phase polymerization, in order to add more hydrogen, the partial pressure of the monomer to be polymerized must be lowered, and in this case, the productivity is lowered. In addition, the use of a large amount of hydrogen also causes cost problems. Therefore, development of a catalyst having a higher effect on the melt flow rate of the so-called hydrogen amount than that of the conventional catalyst has been desired so that a polymer having a high melt flow rate can be produced with a smaller amount of hydrogen. It was not sufficient to fundamentally solve the problem of TPO production due to the direct weight described above.
As a catalyst capable of producing a polymer having a high melt flow rate with a smaller amount of hydrogen, in Patent Document 4 (International Publication WO2004 / 016662 A1), a catalyst solid component essentially comprising magnesium, titanium, a halogen element, and an electron donor, An olefin polymerization or copolymerization catalyst containing an organoaluminum compound and an organosilicon compound represented by Si (OR ¹ ) ₃ (NR ² R ³ ) is described, but such a catalyst is still rare. It is a fact.
That is, the object of the present invention is to maintain a high degree of stereoregularity and yield of the polymer, and to have a great effect on the melt flow rate of the hydrogen amount, so-called good hydrogen response, and a catalyst for polymerization of olefins. Another object of the present invention is to provide a process for producing an olefin polymer.

Under such circumstances, the present inventors have made extensive studies, and as a result, formed from a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound, an organoaluminum compound, and an aminosilane compound having a specific structure. The present inventors have found that the catalyst is more suitable as a catalyst for olefin polymerization than the conventional catalyst described above, and completed the present invention.
That is, the present invention provides (A) a solid catalyst component containing magnesium, titanium, a halogen atom and an electron donating compound,
(B) the following general formula (1);
R ¹ _p AlQ _3-p (1)
(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p ≦ 3), and (C) the following general formula (2);
(R ² NH) ₂ Si (OR ³ ) ₂ (2)
(Wherein, R ² is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group and a derivative thereof, a phenyl group, a vinyl group, an allyl group, in any of the aralkyl groups, which may be the same or different, R ³ is And an aminosilane compound represented by the following general formula (3): an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, and an aralkyl group, which may be the same or different. ;
(R ⁴ NH) R ⁵ Si (OR ⁶ ) ₂ (3)
(Wherein R ⁴ and R ⁵ represent a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group and derivatives thereof, a vinyl group, an allyl group, an aralkyl group, and may be the same or different; R ⁶ is a linear or branched alkyl group having 1 to 12 carbon atoms, which may be the same or different.) And is formed from one or more aminosilane compounds selected from aminosilane compounds represented by The present invention provides a catalyst for olefin polymerization.
The present invention also provides a method for producing an olefin polymer, which is carried out in the presence of the olefin polymerization catalyst.
The catalyst for polymerizing olefins of the present invention can maintain a higher degree of polymer stereoregularity and yield than conventional catalysts, and has a large effect on the melt flow rate of the amount of hydrogen (hereinafter simply referred to as “hydrogen response”). Is obtained). Therefore, it is possible to provide a general-purpose polyolefin at a low cost due to functions such as reduction in the amount of hydrogen used in polymerization and high catalyst activity, and it is expected to be useful in the production of highly functional olefin polymers. The

  FIG. 1 is a flowchart showing steps for preparing the polymerization catalyst of the present invention.

  Among the olefin polymerization catalysts of the present invention, the solid catalyst component (A) (hereinafter sometimes referred to as “component (A)”) contains magnesium, titanium, a halogen atom and an electron donating compound. Specifically, it can be obtained by contacting (a) a magnesium compound, (b) a tetravalent titanium halogen compound and (c) an electron donating compound. Examples of the magnesium compound (hereinafter sometimes simply referred to as “component (a)”) include dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, and fatty acid magnesium. Among these magnesium compounds, magnesium dihalide, a mixture of magnesium dihalide and dialkoxymagnesium, dialkoxymagnesium is preferable, dialkoxymagnesium is particularly preferable, specifically, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, Butoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnes Um, and the like, diethoxy magnesium is particularly preferred.
  These dialkoxymagnesium may be obtained by reacting metal magnesium with alcohol in the presence of a halogen-containing organic metal or the like. The above dialkoxymagnesium can be used alone or in combination of two or more.
  Furthermore, dialkoxymagnesium that is preferably used is in the form of granules or powder, and the shape thereof may be indefinite or spherical. For example, when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution is obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved. Problems such as filter clogging in the polymer separation apparatus due to the fine powder contained are solved.
  The spherical dialkoxymagnesium does not necessarily need to be spherical, and may be oval or potato-shaped. Specifically, the shape of the particles is such that the ratio (L / W) of the major axis diameter L to the minor axis diameter W is 3 or less, preferably 1 to 2, more preferably 1 to 1.5. .
  The dialkoxymagnesium having an average particle size of 1 to 200 μm can be used. Preferably it is 5-150 micrometers. In the case of spherical dialkoxymagnesium, the average particle size is 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 40 μm. Moreover, about the particle size, it is preferable to use a thing with few fine powder and coarse powder and a narrow particle size distribution. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, the particle size of 100 μm or more is 10% or less, preferably 5% or less. Further, when the particle size distribution is represented by D90 / D10 (where D90 is the integrated particle size at 90%, D10 is the integrated particle size at 10%), it is 3 or less, preferably 2 or less. .
  For example, JP-A-58-4132, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A-4-36891 can be used for producing spherical dialkoxymagnesium as described above. It is illustrated in the 8-73388 gazette etc.
  When dialkoxymagnesium is used as component (a), a silicon halide compound such as tetrachlorosilane or trichlorosilane is brought into contact with dialkoxymagnesium before contacting with a tetravalent titanium halogen compound (b) described later. It can also be halogenated.
  The tetravalent titanium halogen compound (b) (hereinafter sometimes referred to as “component (b)”) used for the preparation of the component (A) in the present invention has the general formula; Ti (OR⁷)_nX_4-n(Wherein R⁷Represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, and n is an integer of 0 ≦ n ≦ 4. Or a compound selected from the group consisting of titanium halides and alkoxytitanium halides.
  Specifically, titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide is exemplified as the titanium halide, and methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n- Butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, tri-n-butoxy titanium chloride, etc. Is exemplified. Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used alone or in combination of two or more.
  The electron donating compound (hereinafter sometimes simply referred to as “component (c)”) used in the preparation of the solid catalyst component (A) in the present invention is an organic compound containing an oxygen atom or a nitrogen atom, for example, Organics containing alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, Si-O-C bonds or Si-N-C bonds Examples thereof include silicon compounds.
  Specifically, alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyle ether, diphenyl ether, 9, Ethers such as 9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, Monobutyl butylate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate phenyl, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, etc. Rubonates, diethyl malonate, dipropyl malonate, dibutyl malonate, diisobutyl malonate, dipentyl malonate, dineopentyl malonate, diethyl isopropyl bromomalonate, diethyl butyl bromomalonate, diethyl diisobutyl bromomalonate, diisopromalon Diethyl diethyl, diethyl dibutylmalonate, diethyl diisobutylmalonate, diethyl diisopentylmalonate, diethyl isopropylbutylmalonate, dimethyl isopropylisopentylmalonate, diethyl bis (3-chloro-n-propyl) malonate, bis (3 -Bromo-n-propyl) diethyl malonate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dipropyl adipate, Dicarboxylic acid diesters such as dibutyl pinate, diisodecyl adipate, dioctyl adipate, phthalic acid diester, phthalic acid diester derivatives, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, phthalic acid dichloride, terephthalic acid dichloride Acid chlorides such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde and other aldehydes, methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine and other amines, olefinic acid amides, stearic acid amides and other amides, Nitriles such as acetonitrile, benzonitrile and tolunitrile, isocyanates such as methyl isocyanate and ethyl isocyanate, phenyl alcohol Organosilicon compounds containing Si—O—C bonds, such as coxisilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, bis (alkylamino) dialkoxysilane, bis (cycloalkylamino) Examples thereof include organosilicon compounds containing a Si—N—C bond such as dialkoxysilane, alkyl (alkylamino) dialkoxysilane, dialkylaminotrialkoxysilane, and cycloalkylaminotrialkoxysilane.
  Among the above electron donating compounds, esters, particularly aromatic dicarboxylic acid diesters are preferably used, and phthalic acid diesters and phthalic acid diester derivatives are particularly preferable. Specific examples of these phthalic acid diesters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-isopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, ethyl methyl phthalate, Methyl isopropyl phthalate, ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), ethyl phthalate isobutyl, di-n-pentyl phthalate, diisopentyl phthalate, dineopentyl phthalate, dihexyl phthalate, phthalate Di-n-heptyl acrylate, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate, bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate, di-isodecyl phthalate, Bis (2,2-dimethylheptyl) phthalate, n-butyl phthalate (isohexyl) N-butyl phthalate (2-ethylhexyl), n-pentyl phthalate (hexyl), n-pentyl phthalate (isohexyl), isopentyl phthalate (heptyl), n-pentyl phthalate (2-ethylhexyl), n-phthalate -Pentyl (isononyl), isopentyl phthalate (n-decyl), n-pentyl phthalate (undecyl), isopentyl phthalate (isohexyl), n-hexyl phthalate (2,2-dimethylhexyl), n-hexyl phthalate Isononyl, n-hexyl phthalate (n-decyl), n-heptyl phthalate (2-ethylhexyl), n-heptyl phthalate (isononyl), n-heptyl phthalate (neo-decyl), 2-ethylhexyl phthalate (Isononyl) is exemplified, and there is one kind of these phthalic acid diesters. 2 or more is used.
  Further, as the phthalic acid diester derivative, one or two hydrogen atoms of the benzene ring to which the two ester groups of the above phthalic acid diester are bonded are an alkyl group having 1 to 5 carbon atoms, or a chlorine atom, bromine atom and fluorine. Examples thereof include those substituted with a halogen atom such as an atom. The solid catalyst component prepared using the phthalic acid diester derivative as an electron donating compound can further improve the effect of hydrogen amount on the melt flow rate, that is, the hydrogen response, and the same amount of hydrogen is added during polymerization. Even when the amount is small or small, the melt flow rate of the polymer can be improved. Specifically, dineopentyl 4-methylphthalate, dineopentyl 4-ethylphthalate, 4,5, dineopentyl dimethylphthalate, dineopentyl 4,5-diethylphthalate, diethyl 4-chlorophthalate, di-n-chlorochlorophthalate Butyl, dineopentyl 4-chlorophthalate, diisobutyl 4-chlorophthalate, diisohexyl 4-chlorophthalate, diisooctyl 4-chlorophthalate, diethyl 4-bromophthalate, di-n-butyl 4-bromophthalate, dineopentyl 4-bromophthalate, 4- Diisobutyl bromophthalate, diisohexyl 4-bromophthalate, diisooctyl 4-bromophthalate, diethyl 4,5-dichlorophthalate, di-n-butyl 4,5-dichlorophthalate, diisohexyl 4,5-dichlorophthalate 4,5-dichloro phthalic acid diisooctyl, can be mentioned, of which 4-bromophthalic acid dineopentyl, 4-bromophthalic di -n- butyl, and 4-bromophthalic acid diisobutyl are preferred.
  In addition, it is also preferable to use the above-mentioned esters in combination of two or more. When the total carbon number of the alkyl group of the ester used is 4 or more compared to that of other esters, the esters are combined. Is desirable.
  In the present invention, the above (a), (b), and (c) are contacted in the presence of the aromatic hydrocarbon compound (d) (hereinafter sometimes simply referred to as “component (d)”). The method of preparing the component (A) by the method is a preferred embodiment. Specifically, as the component (d), specifically, an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C. such as toluene, xylene, or ethylbenzene is preferably used. . Moreover, these may be used independently or may be used in mixture of 2 or more types.
  As a particularly preferred method for preparing the component (A) in the present invention, a suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. The preparation method by making the mixed solution formed from b) and component (d) contact this suspension, and making it react after that can be mentioned.
  In the preparation of the solid catalyst component (A) of the present invention, it is preferable to use a polysiloxane (hereinafter sometimes simply referred to as “component (e)”) in addition to the above components. As a result, the stereoregularity or crystallinity of the produced polymer can be improved, and further the fine powder of the produced polymer can be reduced. Polysiloxane is a polymer having a siloxane bond (—Si—O bond) in the main chain, but is also collectively referred to as silicone oil, and has a viscosity at 25 ° C. of 0.02 to 100 cm 2 / s (2 to 10,000 centistokes). It is a liquid or viscous chain, partially hydrogenated, cyclic or modified polysiloxane at room temperature.
  As the chain polysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane are used. As the partially hydrogenated polysiloxane, methylhydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used. As the cyclic polysiloxane, hexamethylcyclotrimethyl is used. Siloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxanes include higher fatty acid groups. Examples thereof include substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, and polyoxyalkylene group-substituted dimethylsiloxane. Among these, decamethylcyclopentasiloxane and dimethylpolysiloxane are preferable, and decamethylcyclopentasiloxane is particularly preferable.
  In the present invention, the components (a), (b), and (c) and, if necessary, the component (d) or the component (e) are contacted to form the component (A). A method for preparing the component (A) will be described. Specifically, the magnesium compound (a) is suspended in a tetravalent titanium halogen compound (b) or an aromatic hydrocarbon compound (d), and an electron-donating compound (c) such as phthalic acid diester is further required. Depending on the method, a method of obtaining a component (A) by contacting a tetravalent titanium halogen compound (b) can be mentioned. In this method, by using a spherical magnesium compound, a spherical component (A) having a sharp particle size distribution can be obtained, and without using the spherical magnesium compound, for example, a solution or suspension can be obtained using a spray device. By forming particles by the so-called spray-drying method in which the turbid liquid is sprayed and dried, the spherical component having a sharp particle size distribution (A) can be obtained.
  The contact of each component is performed with stirring in a container equipped with a stirrer in a state where moisture and the like are removed under an inert gas atmosphere. The contact temperature is the temperature at the time of contact of each component at the time of contact of each component, and may be the same temperature as the reaction temperature or a different temperature. The contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact with stirring and mixed, or is dispersed or suspended for modification, but the product is allowed to react after contact. When obtaining, the temperature range of 40-130 degreeC is preferable. If the temperature during the reaction is less than 40 ° C, the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid catalyst component, and if it exceeds 130 ° C, evaporation of the solvent used becomes remarkable. Therefore, it becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.
  A preferred method for preparing component (A) of the present invention is to suspend component (a) in component (d), then contact component (b), and then contact component (c) and component (d). , A method of preparing component (A) by reacting, or component (a) is suspended in component (d), and then component (c) is contacted and then component (b) is contacted and reacted The method of preparing a component (A) can be mentioned by this. Moreover, the performance of the final solid catalyst component can be improved by bringing the component (A) thus prepared into contact with the component (b) or the component (b) and the component (c) again or multiple times. it can. At this time, it is desirable to carry out in the presence of the aromatic hydrocarbon compound (d).
  As a preferred method for preparing component (A) in the present invention, a suspension is formed from component (a), component (c), and aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and component (b) ) And the component (d) are brought into contact with the suspension and then reacted.
  Preferred methods for preparing component (A) in the present invention include the methods shown below. A suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. A mixed solution is formed from the component (c) and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and the suspension is added to the mixed solution. Then, the obtained mixed solution is heated and subjected to a reaction treatment (first reaction treatment). After completion of the reaction, the obtained solid substance is washed with a liquid hydrocarbon compound at room temperature, and the solid substance after washing is used as a solid product. Thereafter, the washed solid material is further brought into contact with component (b) and an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. at −20 to 100 ° C., and the temperature is raised. The component (A) can also be obtained by repeating the reaction treatment (secondary reaction treatment) and washing with a hydrocarbon compound that is liquid at room temperature after completion of the reaction 1 to 10 times.
  As a more preferable preparation method of the component (A) in the present invention, a suspension obtained by suspending the magnesium compound (a) in the aromatic hydrocarbon compound (d) is used as a tetravalent titanium halogen compound (b). And a mixture solution of the aromatic hydrocarbon compound (d) and then the resulting suspension is contacted with an electron donating compound (c) to obtain a solid product. The method of preparing by contacting the mixed solution of a titanium halogen compound (b) and an aromatic hydrocarbon compound (d) can be mentioned.
  As a more preferable preparation method of the solid catalyst component (A) in the present invention, an ether solution of an alkylmagnesium halide is brought into contact with a homogeneous solution of tetraalkoxytitanium, tetraalkoxysilane and an aliphatic hydrocarbon compound, and the obtained solid An example is a method in which the product is contacted with phthalic acid diester and then further contacted with phthalic acid diester and titanium tetrachloride at least once. More preferably, phthalic acid diester and titanium tetrachloride are contacted twice.
  As a more preferable preparation method of the solid catalyst component (A) in the present invention, the solid component (a) is added to a homogeneous solution obtained by reacting magnesium dihalide, an aliphatic hydrocarbon compound and an alcohol with anhydrous phthalate. A method may be mentioned in which an acid is contacted, titanium tetrachloride is contacted, and then a phthalic acid diester is contacted.
  Based on the above, a particularly preferred method for preparing the solid catalyst component (A) in the present invention is to suspend dialkoxymagnesium (a) in an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. After bringing the tetravalent titanium halogen compound (b) into contact with the suspension, a reaction treatment is performed. At this time, before or after the tetravalent titanium halogen compound (b) is brought into contact with the suspension, one or more electron donating compounds (c) such as phthalic acid diesters are added at −20 to 20 Contact is performed at 130 ° C., and the component (e) is contacted as necessary to carry out a reaction treatment to obtain a solid product (1). At this time, it is desirable to perform the aging reaction at a low temperature before or after contacting one or more of the electron donating compounds. This solid product (1) was washed with a liquid hydrocarbon compound at room temperature (intermediate washing), and then the tetravalent titanium halogen compound (b) was again -20 to 100 ° C in the presence of the aromatic hydrocarbon compound. And a reaction treatment is performed to obtain a solid product (2). If necessary, intermediate cleaning and reaction treatment may be repeated a plurality of times. Next, the solid product (2) is washed with a hydrocarbon compound that is liquid at room temperature by decantation to obtain the solid catalyst component (A).
  The ratio of the amount of each component used in preparing the solid catalyst component (A) varies depending on the preparation method, and thus cannot be determined unconditionally. For example, a tetravalent titanium halogen compound (b) per mole of the magnesium compound (a) Is 0.5 to 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and the electron donating compound (c) is 0.01 to 10 mol, preferably 0.01 to 1 mol. More preferably, it is 0.02 to 0.6 mol, and the aromatic hydrocarbon compound (d) is 0.001 to 500 mol, preferably 0.001 to 100 mol, more preferably 0.005 to 10 mol. The polysiloxane (e) is 0.01 to 100 g, preferably 0.05 to 80 g, more preferably 1 to 50 g.
  Further, the content of titanium, magnesium, halogen atom, and electron donating compound in the solid catalyst component (A) in the present invention is not particularly limited, but preferably titanium is 1.0 to 8.0% by weight, preferably 2 0.0-8.0 wt%, more preferably 3.0-8.0 wt% magnesium is 10-70 wt%, more preferably 10-50 wt%, particularly preferably 15-40 wt%, and still more preferably 15 to 25% by weight, halogen atom 20 to 90% by weight, more preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight, still more preferably 45 to 75% by weight, and the total amount of electron donating compounds is 0 0.5 to 30% by weight, more preferably 1 to 25% by weight, particularly preferably 2 to 20% by weight.
  The organoaluminum compound (B) (hereinafter sometimes simply referred to as “component (B)”) used in forming the olefin polymerization catalyst of the present invention is a compound represented by the above general formula (1). If there is no particular limitation, R¹Is preferably an ethyl group or an isobutyl group, and Q is preferably a hydrogen atom, a chlorine atom or a bromine atom, and p is preferably 2 or 3, particularly preferably 3. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more can be used. Triethylaluminum and triisobutylaluminum are preferable.
  As the aminosilane compound (C) (hereinafter sometimes simply referred to as “component (C)”) used in forming the olefin polymerization catalyst of the present invention, the above general formula (2) or general formula (3) may be used. ) Is used. The aminosilane compound of the general formula (2) is a compound in which an N atom is directly bonded to a Si atom, and the N atom is a hydrogen atom and R²A compound containing a secondary amino group bonded to a group. Examples of such aminosilane compounds include bis (alkylamino) dialkoxysilane, bis (cycloalkylalkylamino) dialkoxysilane, bis (alkyl-substituted cycloalkylamino) dialkoxysilane, and bis (halogen-substituted cycloalkylamino) dialkoxy. Silane, bis (cycloalkylalkylamino) dialkoxysilane and the like are mentioned, and among these, bis (alkylamino) dialkoxysilane and bis (cycloalkylalkylamino) dialkoxysilane are preferable, and bis (t-butylamino) dioxysilane. Alkoxysilane, bis (sec-butylamino) dialkoxysilane, bis (iso-butylamino) dialkoxysilane, bis (iso-propylamino) dialkoxysilane, bis (cyclopentylamino) ) Dialkoxy silane and bis (cyclohexylamino) dialkoxysilane is particularly preferred.
  R in the general formula (2)²Is preferably an alkyl group having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, neo-pentyl group. Group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group and the like. Among these, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, neo- A pentyl group is preferred.
  R²Is preferably a cycloalkyl group having 3 to 12 carbon atoms, specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 3- Propylcyclopentyl group, 3-isopropylcyclopentyl group, 3-butylcyclopentyl group, 3-isobutylcyclopentyl group, 3-t-butylcyclopentyl group, 2,2-dimethylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2,5- Dimethylcyclopentyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 2-ethylcyclohexyl group, 3-propylcyclohexyl group, 3-isopropylcyclohexyl group, 3-butylcyclohexyl group, 3-isobutylcycle Hexyl group, 3-t-butylcyclohexyl group, 2,2-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 1-cyclopentylmethyl group, cyclopentylmethyl group, 1-cyclopentylethyl group 1-cyclopentylpropyl group, menthyl group, mentenyl group, 2-chlorocyclopentyl group, 2-bromocyclopentyl group, 2-chlorocyclohexyl, 2-bromocyclohexyl group and the like. Among these, a cyclopentyl group and a cyclohexyl group are particularly preferable.
  R in the general formula (2)³Is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, A hexyl group, a heptyl group, an octyl group, etc. are mentioned, Among these, a methyl group and an ethyl group are particularly preferable.
  Specific examples of such aminosilane compounds include bis (methylamino) dimethoxysilane, bis (methylamino) diethoxysilane, bis (ethylamino) dimethoxysilane, bis (ethylamino) diethoxysilane, and bis (propylamino). ) Dimethoxysilane, bis (propylamino) diethoxysilane, bis (isopropylamino) dimethoxysilane, bis (isopropylamino) diethoxysilane, bis (butylamino) dimethoxysilane, bis (butylamino) diethoxysilane, bis (isobutyl) Amino) dimethoxysilane, bis (isobutylamino) diethoxysilane, bis (t-butylamino) dimethoxysilane, bis (t-butylamino) diethoxysilane, bis (sec-butylamino) dimethoxysilane, bis (s c-butylamino) diethoxysilane, bis (cyclopentylamino) dimethoxysilane, bis (cyclopentylamino) diethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (cyclohexylamino) diethoxysilane, bis (2-methylcyclopentylamino) ) Dimethoxysilane, bis (2-methylcyclopentylamino) diethoxysilane, bis (2-ethylcyclopentylamino) dimethoxysilane, bis (2-ethylcyclopentylamino) diethoxysilane, bis (2-chlorocyclopentylamino) dimethoxysilane, Bis (2-chlorocyclopentylamino) diethoxysilane, bis (2-bromocyclopentylamino) dimethoxysilane, bis (2-bromocyclopentylamino) diethoxysilane Bis (2-methylcyclohexylamino) dimethoxysilane, bis (2-methylcyclohexylamino) diethoxysilane, bis (2-ethylcyclohexylamino) dimethoxysilane, bis (2-ethylcyclohexylamino) diethoxysilane, bis (2 -Chlorocyclohexylamino) dimethoxysilane, bis (2-chlorocyclohexylamino) diethoxysilane, bis (2-bromocyclohexylamino) dimethoxysilane, bis (2-bromocyclohexylamino) diethoxysilane, bis (cyclopentylmethylamino) dimethoxy Silane, bis (cyclopentylmethylamino) diethoxysilane, bis (1-cyclopentylethylamino) dimethoxysilane, bis (1-cyclopentylethylamino) ditriethoxysila 1 type or 2 types or more can be used. Among these, bis (ethylamino) dimethoxysilane, bis (propylamino) dimethoxysilane, bis (isopropylamino) dimethoxysilane, bis (butylamino) dimethoxysilane, bis (isobutylamino) dimethoxysilane, bis (t- Butylamino) dimethoxysilane, bis (sec-butylamino) diethoxysilane, bis (isobutylamino) diethoxysilane, bis (isopropylamino) diethoxysilane, bis (cyclopentylamino) dimethoxysilane, bis (cyclohexylamino) dimethoxysilane Particularly preferably, bis (t-butylamino) dimethoxysilane, bis (sec-butylamino) diethoxysilane, bis (iso-butylamino) diethoxysilane, bis (iso-propyl) Mino) diethoxy silane, bis (cyclopentylamino) dimethoxysilane, bis (cyclohexylamino) dimethoxysilane.
  The compound represented by the general formula (3) is a compound in which the N atom of the aminosilane compound is directly bonded to the Si atom, and the N atom is a hydrogen atom and R⁴Is combined with. Examples of such aminosilane compounds include alkyl (alkylamino) dialkoxysilanes, alkyl (cycloalkylamino) dialkoxysilanes, alkyl (alkyl group-substituted cycloalkylamino) dialkoxysilanes, and among these, alkyl ( Alkylamino) dialkoxysilane, cycloalkyl (alkylamino) dialkoxysilane, alkyl (cycloalkylamino) dialkoxysilane, decahydronaphthyl (alkylamino) dialkoxysilane, alkyl (alkylamino) dialkoxysilane, cyclo Alkyl (alkylamino) dialkoxysilane and decahydronaphthyl (alkylamino) dialkoxysilane are particularly preferred.
  R in the general formula (3)⁴, R⁵Are preferably an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 3 to 8 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, t- Butyl group, n-pentyl group, isopentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, isooctyl group, 2-methylhexyl group, 2-ethylhexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, Cyclohexyl group and the like, and R⁴, R⁵May be the same or different. Among these, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, hexyl group, cyclopentyl group, cyclohexyl group, 2-methylhexyl Group, decahydronaphthyl group is preferred. R⁵Is preferably an alkyl group having 1 to 5 carbon atoms, in particular an alkyl group having 1 to 5 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, or a t-butyl group. Alkyl groups such as n-pentyl group and neopentyl group, and decahydronaphthyl group are preferred. R⁵Alkyl (t-butylamino) dialkoxysilane, alkyl (iso-propylamino) dialkoxysilane, alkyl (cyclohexylamino) dialkoxysilane, or decahydronaphthyl (alkylamino) dialkoxysilane is more preferred. N-propyl (alkylamino) dialkoxysilane, iso-butyl (alkylamino) dialkoxysilane, cyclopentyl (alkylamino) dialkoxysilane, cyclohexyl (alkylamino) dialkoxysilane, or decahydronaphthyl (alkylamino) dialkyl Alkoxysilane is particularly preferred.
  R in the general formula (3)⁶Is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, A heptyl group, an octyl group, etc. are mentioned, Among these, a methyl group and an ethyl group are especially preferable.
  Specific examples of such aminosilane compounds include decahydronaphthyl (ethylamino) dimethoxysilane, methyl (isopropylamino) dimethoxysilane, ethyl (isopropylamino) dimethoxysilane, n-propyl (isopropylamino) dimethoxysilane, isopropyl ( Isopropylamino) dimethoxysilane, sec-butyl (isopropylamino) dimethoxysilane, t-butyl (isopropylamino) dimethoxysilane, cyclopentyl (isopropylamino) dimethoxysilane, cyclohexyl (isopropylamino) dimethoxysilane, 2-methylcyclohexyl (isopropylamino) Dimethoxysilane, 2,6-dimethylcyclohexyl (isopropylamino) dimethoxysilane, methyl (n-butylamino) Dimethoxysilane, ethyl (n-butylamino) dimethoxysilane, n-propyl (n-butylamino) dimethoxysilane, isopropyl (n-butylamino) dimethoxysilane, Sec-butyl (n-butylamino) dimethoxysilane, t-butyl (N-butylamino) dimethoxysilane, cyclopentyl (n-butylamino) dimethoxysilane, cyclohexyl (n-butylamino) dimethoxysilane, 2-methylcyclohexyl (n-butylamino) dimethoxysilane, 2,6-dimethylcyclohexyl (n -Butylamino) dimethoxysilane, methyl (sec-butylamino) dimethoxysilane, ethyl (sec-butylamino) dimethoxysilane, n-propyl (sec-butylamino) dimethoxysilane, isopropyl (se -Butylamino) dimethoxysilane, t-butyl (sec-butylamino) dimethoxysilane, cyclopentyl (sec-butylamino) dimethoxysilane, 2-methylcyclopentyl (sec-butylamino) dimethoxysilane, cyclohexyl (sec-butylamino) dimethoxy Silane, 2-methylcyclohexyl (sec-butylamino) dimethoxysilane, 2,6-dimethylcyclohexyl (sec-butylamino) dimethoxysilane, methyl (t-butylamino) dimethoxysilane, ethyl (t-butylamino) dimethoxysilane, n-propyl (t-butylamino) dimethoxysilane, isopropyl (t-butylamino) dimethoxysilane, n-butyl (t-butylamino) dimethoxysilane, isobutyl (t-butylamino) ) Dimethoxysilane, sec-butyl (t-butylamino) dimethoxysilane, t-butyl (t-butylamino) dimethoxysilane, cyclopentyl (t-butylamino) dimethoxysilane, cyclohexyl (t-butylamino) dimethoxysilane, 2- Methylcyclohexyl (t-butylamino) dimethoxysilane, 2,6-dimethylcyclohexyl (t-butylamino) dimethoxysilane, methyl (cyclopentylamino) dimethoxysilane, ethyl (cyclopentylamino) dimethoxysilane, n-propyl (cyclopentylamino) dimethoxy Silane, isopropyl (cyclopentylamino) dimethoxysilane, sec-butyl (cyclopentylamino) dimethoxysilane, t-butyl (cyclopentylamino) dimethoxysilane, Clopentyl (cyclopentylamino) dimethoxysilane, cyclohexyl (cyclopentylamino) dimethoxysilane, 2-methylcyclohexyl (cyclopentylamino) dimethoxysilane, methyl (cyclohexylamino) dimethoxysilane, ethyl (cyclohexylamino) dimethoxysilane, n-propyl (cyclohexylamino) Dimethoxysilane, isopropyl (cyclohexylamino) dimethoxysilane, sec-butyl (cyclohexylamino) dimethoxysilane, t-butyl (cyclohexylamino) dimethoxysilane, cyclopentyl (cyclohexylamino) dimethoxysilane, cyclohexyl (cyclohexylamino) dimethoxysilane, 2-methyl Cyclohexyl (cyclohexylamino) dimethoxysilane 2,6-dimethylcyclohexyl (cyclohexylamino) dimethoxysilane, methyl (2-methylcyclohexylamino) dimethoxysilane, ethyl (2-methylcyclohexylamino) dimethoxysilane, n-propyl (2-methylcyclohexylamino) dimethoxysilane, isopropyl ( 2-methylcyclohexylamino) dimethoxysilane, sec-butyl (2-methylcyclohexylamino) dimethoxysilane, t-butyl (2-methylcyclohexylamino) dimethoxysilane, cyclopentyl (2-methylcyclohexylamino) dimethoxysilane, 2-methylcyclopentyl (2-methylcyclohexylamino) dimethoxysilane, cyclohexyl (2-methylcyclohexylamino) dimethoxysilane, 2-methylcyclone Rohexyl (2-methylcyclohexylamino) dimethoxysilane, 2,6-dimethylcyclohexyl (2-methylcyclohexylamino) dimethoxysilane, decahydronaphthyl (methylamino) diethoxysilane, methyl (isopropylamino) diethoxysilane, ethyl (isopropyl) Amino) diethoxysilane, n-propyl (isopropylamino) diethoxysilane, isopropyl (isopropylamino) diethoxysilane, sec-butyl (isopropylamino) diethoxysilane, t-butyl (isopropylamino) diethoxysilane, cyclopentyl ( Isopropylamino) diethoxysilane, cyclohexyl (isopropylamino) diethoxysilane, 2-methylcyclohexyl (isopropylamino) diethoxysilane 2,6-dimethylcyclohexyl (isopropylamino) diethoxysilane, methyl (n-butylamino) diethoxysilane, ethyl (n-butylamino) ditooxysilane, n-propyl (n-butylamino) diethoxysilane, isopropyl (n -Butylamino) diethoxysilane, sec-butyl (n-butylamino) diethoxysilane, t-butyl (n-butylamino) ditooxysilane, cyclopentyl (n-butylamino) diethoxysilane, cyclohexyl (n-butylamino) Diethoxysilane, 2-methylcyclohexyl (n-butylamino) diethoxysilane, 2,6-dimethylcyclohexyl (n-butylamino) diethoxysilane, methyl (n-butylamino) diethoxysilane, methyl (sec-butyl) amino Diethoxysilane, ethyl (sec-butylamino) diethoxysilane, n-propyl (sec-butylamino) diethoxysilane, isopropyl (sec-butylamino) diethoxysilane, cyclopentyl (sec-butylamino) diethoxysilane, Cyclohexyl (sec-butylamino) diethoxysilane, 2-methylcyclohexyl (sec-butylamino) diethoxysilane, 2,6-dimethylcyclohexyl (sec-butylamino) diethoxysilane, methyl (t-butylamino) diethoxy Silane, ethyl (t-butylamino) diethoxysilane, n-propyl (t-butylamino) diethoxysilane, isopropyl (t-butylamino) diethoxysilane, n-butyl (t-butylamino) diethoxysilane, Isobu Til (t-butylamino) diethoxysilane, sec-butyl (t-butylamino) diethoxysilane, t-butyl (t-butylamino) diethoxysilane, cyclopentyl (t-butylamino) diethoxysilane, cyclohexyl ( t-butylamino) diethoxysilane, 2-methylcyclohexyl (t-butylamino) diethoxysilane, 2,6-dimethylcyclohexyl (t-butylamino) diethoxysilane, methyl (cyclopentylamino) diethoxysilane, ethyl ( Cyclopentylamino) diethoxysilane, n-propyl (cyclopentylamino) diethoxysilane, isopropyl (cyclopentylamino) diethoxysilane, sec-butyl (cyclopentylamino) diethoxysilane, t-butyl (cyclopentylamino) ) Diethoxysilane, cyclopentyl (cyclopentylamino) diethoxysilane, cyclohexyl (cyclopentylamino) diethoxysilane, 2-methylcyclohexyl (cyclopentylamino) diethoxysilane, 2,6-dimethyl (cyclopentylamino) diethoxysilane, methyl ( Cyclohexylamino) diethoxysilane, ethyl (cyclohexylamino) diethoxysilane, n-propyl (cyclohexylamino) diethoxysilane, isopropyl (cyclohexylamino) diethoxysilane, sec-butyl (cyclohexylamino) diethoxysilane, t-butyl (Cyclohexylamino) diethoxysilane, cyclopentyl (cyclohexylamino) diethoxysilane, cyclohexyl (cyclohexylamino) di Toxisilane, 2-methylcyclohexyl (cyclohexylamino) diethoxysilane, 2,6-dimethyl (cyclohexylcyclohexylamino) diethoxysilane, methyl (2-methylcyclohexylamino) diethoxysilane, ethyl (2-methylcyclohexylamino) diethoxy Silane, n-propyl (2-methylcyclohexylamino) diethoxysilane, isopropyl (2-methylcyclohexylamino) diethoxysilane, sec-butyl (2-methylcyclohexylamino) diethoxysilane, t-butyl (2-methylcyclohexyl) Amino) diethoxysilane, cyclopentyl (2-methylcyclohexylamino) diethoxysilane, cyclohexyl (2-methylcyclohexylamino) diethoxysilane, 2-methyl Cyclohexyl (2-methylcyclohexylamino) diethoxysilane, 2,6-dimethyl (2-methylcyclohexylcyclohexylamino) diethoxysilane, methyl (isopropylamino) di-n-propoxysilane, ethyl (isopropylamino) di-n- Propoxysilane, n-propyl (isopropylamino) di-n-propoxysilane, isopropyl (isopropylamino) di-n-propoxysilane, sec-butyl (isopropylamino) di-n-propoxysilane, t-butyl (isopropylamino) Di-n-propoxysilane, cyclopentyl (isopropylamino) di-n-propoxysilane, cyclohexyl (isopropylamino) di-n-propoxysilane, 2-methylcyclohexyl (isopropylamino) -N-propoxysilane, 2,6-dimethylcyclohexyl (isopropylamino) di-n-propoxysilane, methyl (n-butylamino) di-n-propoxysilane, ethyl (n-butylamino) di-n-propoxysilane , N-propyl (n-butylamino) di-n-propoxysilane, isopropyl (n-butylamino) di-n-propoxysilane, sec-butyl (n-butylamino) di-n-propoxysilane, t-butyl (N-butylamino) di-n-propoxysilane, cyclopentyl (n-butylamino) di-n-propoxysilane, cyclohexyl (n-butylamino) di-n-propoxysilane, 2-methylcyclohexyl (n-butylamino) ) Di-n-propoxysilane, 2,6-dimethylcyclohexyl (n- Tilamino) di-n-propoxysilane, methyl (sec-butylamino) di-n-propoxysilane, ethyl (sec-butylamino) di-n-propoxysilane, n-propyl (sec-butylamino) di-n- Propoxysilane, isopropyl (sec-butylamino) di-n-propoxysilane, sec-butyl (sec-butylamino) di-n-propoxysilane, t-butyl (sec-butylamino) di-n-propoxysilane, cyclopentyl (Sec-butylamino) di-n-propoxysilane, cyclohexyl (sec-butylamino) di-n-propoxysilane, 2-methylcyclohexyl (sec-butylamino) di-n-propoxysilane, 2,6-dimethylcyclohexyl (Sec-Butylamino) di-n-pro Poxysilane, methyl (t-butylamino) di-n-propoxysilane, ethyl (t-butylamino) di-n-propoxysilane, n-propyl (t-butylamino) di-n-propoxysilane, isopropyl (t- Butylamino) di-n-propoxysilane, n-butyl (t-butylamino) di-n-propoxysilane, sec-butyl (t-butylamino) di-n-propoxysilane, t-butyl (t-butylamino) ) Di-n-propoxysilane, cyclopentyl (t-butylamino) di-n-propoxysilane, cyclohexyl (t-butylamino) di-n-propoxysilane, 2-methylcyclohexyl (t-butylamino) di-n- Propoxysilane, 2,6-dimethylcyclohexyl (t-butylamino) di-n-propoxy , Methyl (cyclopentylamino) di-n-propoxysilane, ethyl (cyclopentylamino) di-n-propoxysilane, n-propyl (cyclopentylamino) di-n-propoxysilane, isopropyl (cyclopentylamino) di-n-propoxy Silane, sec-butyl (cyclopentylamino) di-n-propoxysilane, t-butyl (cyclopentylamino) di-n-propoxysilane, cyclopentyl (cyclopentylamino) di-n-propoxysilane, cyclohexyl (cyclopentylamino) di-n -Propoxysilane, 2-methylcyclohexyl (cyclopentylamino) di-n-propoxysilane, 2,6-dimethyl (cyclopentylamino) di-n-propoxysilane, methyl (cyclohexylamino) di n-propoxysilane, ethyl (cyclohexylamino) di-n-propoxysilane, n-propyl (cyclohexylamino) di-n-propoxysilane, isopropyl (cyclohexylamino) di-n-propoxysilane, sec-butyl (cyclohexylamino) Di-n-propoxysilane, t-butyl (cyclohexylamino) di-n-propoxysilane, cyclopentyl (cyclohexylamino) di-n-propoxysilane, cyclohexyl (cyclohexylamino) di-n-propoxysilane, 2-methylcyclohexyl ( Cyclohexylamino) di-n-propoxysilane, 2,6-dimethyl (cyclohexylcyclohexylamino) di-n-propoxysilane, methyl (2-methylcyclohexylamino) di-n-propoxy Silane, ethyl (2-methylcyclohexylamino) di-n-propoxysilane, n-propyl (2-methylcyclohexylamino) di-n-propoxysilane, isopropyl (2-methylcyclohexylamino) di-n-propoxysilane, sec -Butyl (2-methylcyclohexylamino) di-n-propoxysilane, t-butyl (2-methylcyclohexylamino) di-n-propoxysilane, cyclopentyl (2-methylcyclohexylamino) di-n-propoxysilane, 2- Methylcyclopentyl (2-methylcyclohexylamino) di-n-propoxysilane, cyclohexyl (2-methylcyclohexylamino) di-n-propoxysilane, 2-methylcyclohexyl (2-methylcyclohexylamino) di-n-propo Sisilane, 2,6-dimethyl (2-methylcyclohexylcyclohexylamino) di-n-propoxysilane, decahydronaphthyl (2-methylcyclohexylamino) di-n-propoxysilane, 1,2,3,4-tetrahydronaphthyl ( 2-methylcyclohexylamino) diethoxysilane, of which ethyl (t-butylamino) dimethoxysilane, ethyl (t-butylamino) diethoxysilane, n-propyl (t-butylamino) diethoxysilane , Isobutyl (t-butylamino) diethoxysilane, isobutyl (t-butylamino) dimethoxysilane, ethyl (isopropylamino) diethoxysilane, ethyl (cyclohexylamino) diethoxysilane, cyclohexyl (t-butylamino) dimethoxysilane Cyclopentyl (isopropyl amino) diethoxy silane, decahydronaphthyl (ethylamino) dimethoxysilane, decahydronaphthyl (methylamino) diethoxy silane are preferred.
  In the olefin polymerization catalyst of the present invention, an electron donating compound other than the above-mentioned aminosilane compound (hereinafter sometimes simply referred to as “component (D)”) can be used in addition to the above components. Specifically, the same electron donating compound (c) used in the preparation of the solid catalyst component (A) can be used, and is an organic compound containing an oxygen atom or a nitrogen atom, such as alcohols, phenols, Examples include ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, and organosilicon compounds containing a Si—O—C bond. Preferred are organosilicon compounds and ethers such as 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, and the organosilicon compounds include the following general silicon compounds: Formula R⁸ _qSi (OR⁹)_4-q(Wherein R⁸Represents hydrogen or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, an aralkyl group, an alkylamino group, a cycloalkylamino group, and a polycyclic amino group, which are the same or different. Well, R⁹Represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, which may be the same or different, and q is an integer of 1 to 3. ) Or one or more of organosilicon compounds (hereinafter sometimes simply referred to as “organosilicon compounds (D)”).
  Specifically, alkyl alkoxy silane, alkyl (cycloalkyl) alkoxy silane, cycloalkyl alkoxy silane, phenyl alkoxy silane, alkyl (phenyl) alkoxy silane, alkyl (alkyl amino) alkoxy silane, alkyl amino alkoxy silane, cycloalkyl (alkyl Amino) alkoxysilane, alkyl (cycloalkylamino) alkoxysilane, polycyclic aminoalkoxysilane, alkyl (polycyclic amino) alkoxysilane and the like can be mentioned.
  Specific examples of the organosilicon compound (D) include di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, and t-butyl (methyl). Dimethoxysilane, t-butyl (ethyl) dimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyl (methyl) dimethoxysilane, dicyclopentyldimethoxysilane, cyclopentyl (methyl) diethoxysilane, cyclopentyl (ethyl) dimethoxysilane, cyclopentyl (cyclohexyl) dimethoxysilane, 3-methylcyclohexyl (cyclopentyl) dimethoxysilane, 4-methylcyclohexyl (cyclopentyl) dimethoxysilane, 3,5-dimethylcyclohexyl (cyclopentyl) Dimethoxysilane, bis (diethylamino) dimethoxysilane, bis (di-n-propylamino) dimethoxysilane, bis (di-n-butylamino) dimethoxysilane, bis (di-t-butylamino) dimethoxysilane, bis (dicyclopentyl) Amino) dimethoxysilane, bis (dicyclohexylamino) dimethoxysilane, bis (di-2-methylcyclohexylamino) dimethoxysilane, bis (isoquinolino) dimethoxysilane, bis (quinolino) dimethoxysilane, bis (ethyl-n-propylamino) dimethoxy Silane, bis (ethylisopropylamino) dimethoxysilane, bis (ethyl-n-butylamino) dimethoxysilane, bis (ethylisobutylamino) dimethoxysilane, bis (ethyl-t-butylamino) dimeth Sisilane, bis (isobutyl-n-propylamino) dimethoxysilane, bis (ethylcyclopentylamino) dimethoxysilane, bis (ethylcyclohexylamino) dimethoxysilane, ethyl (diethylamino) dimethoxysilane, n-propyl (diisopropylamino) dimethoxysilane, isopropyl (Di-t-butylamino) dimethoxysilane, cyclohexyl (diethylamino) dimethoxysilane, ethyl (di-t-butylamino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, n-propyl (isoquinolino) dimethoxysilane, isopropyl (isoquinolino) Dimethoxysilane, n-butyl (isoquinolino) dimethoxysilane, ethyl (quinolino) dimethoxysilane, n-propyl (quinolino) dimethoxysilane Lan, isopropyl (quinolino) dimethoxysilane, n-butyl (quinolino) dimethoxysilane, bis (diethylamino) diethoxysilane, bis (di-n-propylamino) diethoxysilane, bis (di-n-butylamino) diethoxy Silane, bis (di-t-butylamino) diethoxysilane, bis (dicyclopentylamino) diethoxysilane, bis (dicyclohexylamino) diethoxysilane, bis (di-2-methylcyclohexylamino) diethoxysilane, bis ( Diisoquinolino) diethoxysilane, bis (diquinolino) diethoxysilane, bis (ethyl-n-propylamino) diethoxysilane, bis (ethylisopropylamino) diethoxysilane, bis (ethyl-n-butylamino) diethoxysilane, Bis (ethyl- Sobutylamino) diethoxysilane, bis (ethyl-t-butylamino) diethoxysilane, bis (isobutyl-n-propylamino) diethoxysilane, bis (ethylcyclopentylamino) diethoxysilane, bis (ethylcyclohexylamino) diethoxy Silane, n-propyl (diisopropylamino) diethoxysilane, ethyl (isoquinolino) diethoxysilane, n-propyl (isoquinolino) diethoxysilane, isopropyl (isoquinolino) diethoxysilane, n-butyl (isoquinolino) diethoxysilane, ethyl (Quinolino) diethoxysilane, n-propyl (quinolino) diethoxysilane, isopropyl (quinolino) diethoxysilane, n-butyl (quinolino) diethoxysilane, texyltrimethoxysilane, di Tilaminotrimethoxysilane, di-n-propylaminotrimethoxysilane, di-n-butylaminotrimethoxysilane, di-t-butylaminotrimethoxysilane, dicyclopentylaminotrimethoxysilane, dicyclohexylaminotrimethoxysilane, di 2-methylcyclohexylaminotrimethoxysilane, isoquinolinotrimethoxysilane, quinolinotrimethoxysilane, diethylaminotriethoxysilane, di-n-propylaminotriethoxysilane, di-n-butylaminotriethoxysilane, ethyl- t-butylaminotriethoxysilane, ethyl-sec-butylaminotriethoxysilane, dicyclopentylaminotriethoxysilane, dicyclohexylaminotriethoxysilane, di-2-methylcyclohexyl Silaminotriethoxysilane, isoquinolinotriethoxysilane, quinolinotriethoxysilane, bis (t-butylamino) dimethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (t-butylamino) diethoxysilane, bis ( (Cyclohexylamino) diethoxysilane, trivinylmethylsilane, and tetravinylsilane are preferably used. Component (D) can be used alone or in combination of two or more.
  When the component (D) is used in combination, preferred combinations with the component (C) include dialkyl dialkoxysilane and bis (alkylamino) dialkoxysilane, dicycloalkyl dialkoxysilane and bis (alkylamino) dialkoxysilane. Bis (isoquinolino) dimethoxysilane and bis (alkylamino) dialkoxysilane, dialkyl dialkoxysilane and alkyl (alkylamino) dialkoxysilane, dicycloalkyl dialkoxysilane and alkyl (alkylamino) dialkoxysilane, bis (isoquinolino) ) Dimethoxysilane and alkyl (alkylamino) dialkoxysilane, etc. Specific combinations include di-isopropyldimethoxysilane and bis (ethylamino) diethoxysilane, t-butyl (methyl) Methoxysilane and bis (ethylamino) diethoxysilane, t-butyl (ethyl) dimethoxysilane and bis (ethylamino) diethoxysilane, cyclohexyl (methyl) dimethoxysilane and bis (ethylamino) diethoxysilane, dicyclopentyldimethoxysilane And bis (ethylamino) diethoxysilane, cyclopentyl (cyclohexyl) dimethoxysilane and bis (ethylamino) diethoxysilane, bis (isoquinolino) dimethoxysilane and bis (ethylamino) diethoxysilane, bis (quinolino) dimethoxysilane and bis (Ethylamino) diethoxysilane, texyltrimethoxysilane and bis (ethylamino) diethoxysilane, di-isopropyldimethoxysilane and bis (t-butylamino) diethoxysilane, t- Til (methyl) dimethoxysilane and bis (t-butylamino) diethoxysilane, dicyclopentyldimethoxysilane and bis (cyclopentylamino) diethoxysilane, t-butyl (ethyl) dimethoxysilane and bis (cyclopentylamino) diethoxysilane, Di-isopropyldimethoxysilane and ethyl (t-butylamino) dimethoxysilane, di-isopropyldimethoxysilane and n-propyl (t-butylamino) diethoxysilane, di-isopropyldimethoxysilane and cyclohexyl (t-butylamino) dimethoxysilane Cyclohexyl (methyl) dimethoxysilane and ethyl (t-butylamino) dimethoxysilane, cyclohexyl (methyl) dimethoxysilane and n-propyl (t-butylamino) diethoxysilane, Cyclohexyl (methyl) dimethoxysilane and cyclohexyl (t-butylamino) dimethoxysilane, dicyclopentyldimethoxysilane and ethyl (t-butylamino) dimethoxysilane, dicyclopentyldimethoxysilane and n-propyl (t-butylamino) diethoxysilane, Dicyclopentyldimethoxysilane and cyclohexyl (t-butylamino) dimethoxysilane, bis (isoquinolino) dimethoxysilane and ethyl (t-butylamino) dimethoxysilane, bis (isoquinolino) dimethoxysilane and n-propyl (t-butylamino) diethoxy Examples thereof include silane, bis (isoquinolino) dimethoxysilane and cyclohexyl (t-butylamino) dimethoxysilane.
  In the presence of the olefin polymerization catalyst of the present invention, homopolymerization, random copolymerization or block copolymerization of olefins is carried out. Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. These olefins can be used alone or in combination of two or more. In particular, ethylene, propylene, and 1-butene are preferably used. Particularly preferred is propylene. In the case of propylene, it can be copolymerized with other olefins. Examples of the olefin to be copolymerized include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like, and these olefins can be used alone or in combination of two or more. . In particular, ethylene and 1-butene are preferably used. Copolymerization of propylene with other olefins includes random copolymerization in one stage using propylene and a small amount of ethylene as a comonomer, and homopolymerization of propylene in the first stage (first polymerization tank). The so-called propylene-ethylene block copolymerization in which propylene and ethylene are copolymerized in a stage (second polymerization tank) or more stages (multistage polymerization tank) is typical. Even in such random copolymerization and block copolymerization, the catalyst of the present invention comprising the component (A), the component (B) and the component (C) is effective, and has catalytic activity, stereoregularity and / or hydrogen. Not only is the response good, but the copolymerization properties and the properties of the resulting copolymer are also good. In particular, the component (D) described above in addition to the component (C) which is the catalyst component of the present invention is mixed and used, or the component (C) and the component (D) are separately used in a block copolymerization multistage polymerization tank. It can also be used. Also, alcohols can be added to the polymerization system in order to prevent gel formation in the final product, especially when shifting from homopolymerization of propylene to block copolymerization. Specific examples of alcohols include ethyl alcohol, isopropyl alcohol and the like, and the amount used is 0.01 to 10 mol, preferably 0.1 to 2 mol, per 1 mol of component (B).
  The use amount ratio of each component is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the component (B) is used per 1 mole of the titanium atom in the component (A). , 1 to 2000 mol, preferably 50 to 1000 mol. Component (C) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.1 to 0.5 mol, per mol of component (B). When component (D) is used in combination, 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, is used per mol of component (B). Further, it is used in an amount of 0.001 to 10 mol, preferably 0.01 to 10 mol, particularly preferably 0.01 to 2 mol, per mol of the component (C).
  The order of contact of each component is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, and then the aminosilane compound (C) is contacted or premixed with the component (C) and the component (D It is desirable to contact the solid catalyst component (A) by contacting the component (C) and the component (D) in any order. Alternatively, the organoaluminum compound (B) is first charged into the polymerization system, while the component (A) and the component (C), or the component (C) and the component (D) are contacted in advance, and the components are brought into contact with each other. It is also a preferred embodiment that (A) and component (C) or component (C) and component (D) are charged into and contacted with each other to form a catalyst. Thus, it is possible to further improve the hydrogen response of the catalyst and the crystallinity of the produced polymer by previously treating the component (A) with the component (B) or the component (C) and the component (D). Become.
  The polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used for polymerization in any state of gas and liquid. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 6 MPa or lower. In addition, either a continuous polymerization method or a batch polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage, or may be performed in two or more stages.
  Furthermore, in polymerizing olefins using the catalyst formed from component (A), component (B) and component (C) in the present invention (also referred to as “main polymerization”), catalytic activity, stereoregularity and production In order to further improve the particle properties and the like, it is desirable to perform prepolymerization prior to the main polymerization. In the preliminary polymerization, monomers similar to the main polymerization such as olefins or styrene can be used. Specifically, component (A), component (B) and / or component (C) are contacted in the presence of olefins, and 0.1 to 100 g of polyolefin per 1 g of component (A) is preliminarily polymerized. Further, the component (B) and / or the component (C) is further contacted to form a catalyst. When component (D) is used in combination, component (A), component (B) and component (D) are brought into contact with each other in the presence of olefins during the preliminary polymerization, and component (C) is used during the main polymerization. You can also.
  In conducting the prepolymerization, the order of contacting the respective components and monomers is arbitrary. Preferably, the component (B) is first placed in a prepolymerization system set in an inert gas atmosphere or a gas atmosphere in which propylene is polymerized. And then contact component (C) and / or component (D), then contact component (A), and then contact olefin such as propylene and / or one or more other olefins. Let The prepolymerization temperature is arbitrary and is not particularly limited, but is preferably in the range of -10 ° C to 70 ° C, more preferably in the range of 0 ° C to 50 ° C.
  When olefins are polymerized in the presence of the olefin polymerization catalyst of the present invention, high stereoregularity is maintained and hydrogen response is improved as compared with the case of using a conventional catalyst. Further, depending on the structure of the component (C), the catalytic activity and stereoregularity are improved as compared with the case where a conventional catalyst is used. That is, when the catalyst of the present invention is used for the polymerization of olefins, the structure of component (C) maintains high stereoregularity, improves hydrogen response, and improves catalytic activity and stereoregularity. Was confirmed.

以上の結果から、重合時にアミノシラン化合物を用いると、高い立体規則性の重合体を収率良く得られ、かつ水素レスポンスが良好であることがわかる。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.
Example 1
<Preparation of solid catalyst component>
A 2000-ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 150 g of diethoxymagnesium and 750 ml of toluene to form a suspension. The suspension was then added to a solution of 450 ml of toluene and 300 ml of titanium tetrachloride, pre-charged in a 2000 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas. The suspension was then reacted at 5 ° C. for 1 hour. Thereafter, 22.5 ml of n-butyl phthalate was added and the temperature was raised to 100 ° C., followed by reaction treatment with stirring for 2 hours. After completion of the reaction, the product was washed four times with 1300 ml of toluene at 80 ° C., 1200 ml of toluene and 300 ml of titanium tetrachloride were newly added, and the reaction treatment was performed at 110 ° C. for 2 hours with stirring. The intermediate wash and the second treatment were repeated once more. The product was then washed 7 times with 1300 ml of 40 ° C. heptane, filtered and dried to obtain a powdered solid catalyst component. The titanium content in the solid component was measured and found to be 3.1% by weight.
<Formation and polymerization of polymerization catalyst>
In an autoclave with a stirrer having an internal volume of 2.0 liters completely substituted with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of bis (t-butylamino) dimethoxysilane and 0.0026 mmol of the solid catalyst component as titanium atoms Charged to form a polymerization catalyst. Thereafter, 1.5 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, then heated up, and polymerized at 70 ° C. for 1 hour. The obtained polymer was measured for catalyst activity, boiling heptane insoluble matter (HI, wt%), and melt flow rate (MI, g-PP / 10 min). The results are shown in Table 1.
The catalyst activity indicating the amount of polymer produced (F) g per hour of the polymerization time per 1 g of the solid catalyst component was calculated by the following equation.
Catalyst activity = product polymer (F) g / solid catalyst component g / 1 hour In addition, after continuously extracting this polymer with boiling n-heptane for 6 hours, the polymer (G) insoluble in n-heptane is dried. Thereafter, the weight was measured, and the proportion of boiling heptane insoluble matter (HI, wt%) in the polymer was calculated from the following equation.
HI (% by weight) = (G) g / (F) g × 100
Method for measuring xylene-soluble component: 4.0 g of a polymer was charged into 200 ml of para-xylene, and the polymer was dissolved at a boiling point (138 ° C.) over 2 hours. Thereafter, the mixture was cooled to 23 ° C., and the dissolved component and the insoluble component were separated by filtration. The dissolved component was dried by heating, and the resulting polymer was defined as xylene-soluble component (XS) (% by weight). The melt index (MI) value indicating the melt flow rate of the polymer was measured according to ASTM D 1238 and JIS K 7210.
Example 2
The experiment was conducted in the same manner as in Example 1 except that 1.5 liters of hydrogen gas was changed to 4.0 liters in the formation of the polymerization catalyst and the polymerization. The obtained results are shown in Table 1.
Example 3
A solid catalyst component was prepared and polymerized in the same manner as in Example 1 except that the polymerization catalyst was formed and polymerized using bis (sec-butylamino) diethoxysilane instead of bis (t-butylamino) dimethoxysilane. Catalyst formation and polymerization were performed. The obtained results are shown in Table 1.
Example 4
A solid catalyst component was prepared and polymerized in the same manner as in Example 1 except that the polymerization catalyst was formed and polymerized using bis (iso-butylamino) diethoxysilane instead of bis (t-butylamino) dimethoxysilane. Catalyst formation and polymerization were performed. The obtained results are shown in Table 1.
Example 5
A solid catalyst component was prepared and polymerized in the same manner as in Example 1 except that the polymerization catalyst was formed and polymerized using bis (iso-propylamino) diethoxysilane instead of bis (t-butylamino) dimethoxysilane. Catalyst formation and polymerization were performed. The obtained results are shown in Table 1.
Example 6
A solid catalyst component was prepared in the same manner as in Example 1 except that the polymerization catalyst was formed and polymerized using bis (cyclopentylamino) dimethoxysilane instead of bis (t-butylamino) dimethoxysilane. Formation and polymerization took place. The obtained results are shown in Table 1.
Example 7
A solid catalyst component was prepared in the same manner as in Example 1 except that the polymerization catalyst was formed and polymerized using bis (cyclohexylamino) dimethoxysilane instead of bis (t-butylamino) dimethoxysilane. Formation and polymerization took place. The obtained results are shown in Table 1.
Example 8
A solid catalyst component was prepared in the same manner as in Example 2 except that ethyl (t-butylamino) dimethoxysilane was used instead of bis (t-butylamino) dimethoxysilane to form a polymerization catalyst. And polymerization was carried out. The obtained results are shown in Table 1.
Example 9
The polymerization catalyst was formed under the same conditions as in Example 2 except that the polymerization catalyst was formed and polymerized using ethyl (t-butylamino) diethoxysilane instead of bis (t-butylamino) dimethoxysilane. Polymerization was performed. The obtained results are shown in Table 1.
Example 10
The polymerization catalyst was prepared under the same conditions as in Example 2 except that the polymerization catalyst was formed and polymerized using n-propyl (t-butylamino) diethoxysilane instead of bis (t-butylamino) dimethoxysilane. Formation and polymerization took place. The obtained results are shown in Table 1.
Example 11
In the same conditions as in Example 2 except that isobutyl (t-butylamino) diethoxysilane was used instead of bis (t-butylamino) dimethoxysilane to form and polymerize the polymerization catalyst, Polymerization was performed. The obtained results are shown in Table 1.
Example 12
Formation of polymerization catalyst and polymerization under the same conditions as in Example 2 except that isobutyl (t-butylamino) dimethoxysilane was used instead of bis (t-butylamino) dimethoxysilane to form and polymerize the polymerization catalyst. Went. The obtained results are shown in Table 1.
Example 13
The polymerization catalyst was formed and polymerized under the same conditions as in Example 2 except that the polymerization catalyst was formed and polymerized using ethyl (isopropylamino) diethoxysilane instead of bis (t-butylamino) dimethoxysilane. went. The obtained results are shown in Table 1.
Example 14
The polymerization catalyst was formed and polymerized under the same conditions as in Example 2 except that the polymerization catalyst was formed and polymerized using ethyl (cyclohexylamino) diethoxysilane instead of bis (t-butylamino) dimethoxysilane. went. The obtained results are shown in Table 1.
Example 15
Formation of polymerization catalyst and polymerization under the same conditions as in Example 2 except that cyclohexyl (t-butylamino) dimethoxysilane was used instead of bis (t-butylamino) dimethoxysilane to form and polymerize the polymerization catalyst. Went. The obtained results are shown in Table 1.
Example 16
A polymerization catalyst was formed and polymerized under the same conditions as in Example 2 except that the polymerization catalyst was formed and polymerized using cyclopentyl (isopropylamino) diethoxysilane instead of bis (t-butylamino) dimethoxysilane. went. The obtained results are shown in Table 1.
Example 17
A polymerization catalyst was formed and polymerized under the same conditions as in Example 8 except that the hydrogen gas amount was 8 liters instead of the 4 liters during polymerization. The obtained results are shown in Table 1.
Example 18
<Preparation of solid catalyst component>
32 g of ground magnesium for Grignard was charged into a 1000 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas. Next, a mixed liquid of 120 g of butyl chloride and 500 ml of dibutyl ether was dropped into the magnesium over 4 hours at 50 ° C., and then reacted at 60 ° C. for 1 hour. After completion of the reaction, the reaction solution was cooled to room temperature and solid content was removed by filtration to obtain a magnesium compound solution. Next, a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 240 ml of hexane, 5.4 g of tetrabutoxytitanium and 61.4 g of tetraethoxysilane to obtain a homogeneous solution. The magnesium compound solution (150 ml) was added dropwise at 5 ° C. over 4 hours to react, and then stirred at room temperature for 1 hour. Next, the reaction solution was filtered at room temperature to remove the liquid portion, and then the remaining solid was washed 8 times with 240 ml of hexane and dried under reduced pressure to obtain a solid product. Then, 8.6 g of the solid product was charged into a 100-ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and further 48 ml of toluene and 5.8 ml of diisobutyl phthalate were added. The reaction was allowed to proceed for 1 hour at ° C. Thereafter, the liquid part was removed by filtration, and the remaining solid was washed 8 times with 85 ml of toluene. After completion of washing, 21 ml of toluene, 0.48 ml of diisobutyl phthalate and 12.8 ml of titanium tetrachloride were added to the flask and reacted at 95 ° C. for 8 hours. After completion of the reaction, solid-liquid separation is performed at 95 ° C., and the solid content is washed twice with 48 ml of toluene. Then, the treatment with the above mixture of diisobutyl phthalate and titanium tetrachloride is performed again under the same conditions, and washed with 48 ml of hexane eight times. Filtered and dried to obtain a powdered solid catalyst component. The titanium content in the solid catalyst component was measured and found to be 2.1% by weight.
<Formation and polymerization of polymerization catalyst>
A polymerization catalyst was formed and polymerized in the same manner as in Example 8 except that the solid catalyst component obtained above was used. The obtained results are shown in Table 1.
Example 19
<Preparation of solid catalyst component>
A 500 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas was charged with 4.76 g of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml of 2-ethylhexyl alcohol, and at 130 ° C. for 2 hours. Reaction was performed to obtain a homogeneous solution. Next, 1.11 g of phthalic anhydride was added to the homogeneous solution and reacted at 130 ° C. for 1 hour. The solution was then added dropwise to 200 ml of titanium tetrachloride charged in a 500 ml round bottom flask equipped with a stirrer and fully substituted with nitrogen gas and maintained at -20 ° C over 1 hour. did. Subsequently, after heating up this mixed solution to 110 degreeC over 4 hours, 2.68 ml of diisobutyl phthalate was added and it was made to react for 2 hours. After completion of the reaction, the liquid part is removed by filtration, and the remaining solid component is washed with decane and hexane at 110 ° C. until no free titanium compound is detected, filtered and dried to obtain a powdered solid catalyst component. It was. The titanium content in the solid catalyst component was measured and found to be 3.1% by weight.
<Formation and polymerization of polymerization catalyst>
A polymerization catalyst was formed and polymerized in the same manner as in Example 8 except that the solid catalyst component obtained above was used. The obtained results are shown in Table 1.
Example 20
Formation of polymerization catalyst and polymerization under the same conditions as in Example 2 except that decahydronaphthyl (ethylamino) dimethoxysilane was used instead of bis (t-butylamino) dimethoxysilane to form and polymerize the polymerization catalyst. Was done. The obtained results are shown in Table 1.
Example 21
The polymerization catalyst was formed under the same conditions as in Example 2 except that the polymerization catalyst was formed and polymerized using decahydronaphthyl (methylamino) diethoxysilane instead of bis (t-butylamino) dimethoxysilane. Polymerization was performed. The obtained results are shown in Table 1.
Comparative Example 1
A solid catalyst component was prepared in the same manner as in Example 1 except that cyclohexylmethyldimethoxysilane was used instead of bis (t-butylamino) dimethoxysilane to form and polymerize, and formation and polymerization of the polymerization catalyst were conducted. Was done. The obtained results are shown in Table 1.
Comparative Example 2
Experiments were performed in the same manner as in Comparative Example 1 except that 1.5 liters of hydrogen gas was changed to 4.0 liters in the formation and polymerization of the polymerization catalyst. The obtained results are shown in Table 1.
Comparative Example 3
Experiments were conducted in the same manner as in Comparative Example 1 except that 1.5 liters of hydrogen gas was changed to 8.0 liters in the formation and polymerization of the polymerization catalyst. The obtained results are shown in Table 1.
Comparative Example 4
Solid catalyst component as in Example 1, except that bis (diethylamino) dimethoxysilane was used instead of bis (t-butylamino) dimethoxysilane to form a polymerization catalyst, and the amount of hydrogen gas during polymerization was 8 liters. Was prepared, and a polymerization catalyst was formed and polymerized. The obtained results are shown in Table 1.
Comparative Example 5
A solid catalyst component was prepared in the same manner as in Example 2 except that diethylaminotriethoxysilane was used instead of bis (t-butylamino) dimethoxysilane to form a polymerization catalyst, and the polymerization catalyst was formed. Polymerization was performed. The obtained results are shown in Table 1.
Comparative Example 6
A solid catalyst component was prepared in the same manner as in Example 18 except that cyclohexylmethyldimethoxysilane was used in place of bis (t-butylamino) dimethoxysilane to form a polymerization catalyst, and the polymerization catalyst was formed. Polymerization was performed. The obtained results are shown in Table 1.
Comparative Example 7
A solid catalyst component was prepared in the same manner as in Example 19 except that cyclohexylmethyldimethoxysilane was used instead of ethyl (t-butylamino) dimethoxysilane to form a polymerization catalyst, and polymerization catalyst formation and polymerization were performed. Polymerization was performed. The obtained results are shown in Table 1.

From the above results, it can be seen that when an aminosilane compound is used at the time of polymerization, a polymer with high stereoregularity can be obtained in good yield and the hydrogen response is good.

  The catalyst for olefin polymerization of the present invention exhibits higher activity against hydrogen and can obtain an olefin polymer in a high yield while maintaining high stereoregularity at a high level. Therefore, general-purpose polyolefin can be provided at low cost, and usefulness is expected in the production of copolymers of olefins having high functionality.

Claims (12)

(A) a solid catalyst component containing magnesium, titanium, a halogen atom and an electron donating compound;
(B) the following general formula (1);
R ¹ _p AlQ _3-p (1)
(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p ≦ 3), and (C) the following general formula (2);
(R ² NH) ₂ Si (OR ³ ) ₂ (2)
(Wherein R ² is any one of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group , an alkyl-substituted cycloalkyl group, a halogen-substituted cycloalkyl group , a phenyl group, a vinyl group, an allyl group, and an aralkyl group, or the same or And R ³ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different. A compound, and the following general formula (3);
(R ⁴ NH) R ⁵ Si (OR ⁶ ) ₂ (3)
( Wherein R ⁴ represents a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, or an alkyl-substituted cycloalkyl group , and R ⁵ represents a linear or branched alkyl group having 1 to ⁵ carbon atoms, A cycloalkyl group having 3 to 8 carbon atoms, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, and R ⁶ is a linear or branched alkyl group having 1 to 12 carbon atoms, which is the same or different. The olefin polymerization catalyst is formed from one or more aminosilane compounds selected from aminosilane compounds represented by:   The olefins according to claim 1, wherein the solid catalyst component is prepared by contacting a magnesium compound (a), a tetravalent titanium halogen compound (b) and an electron donating compound (c). Polymerization catalyst.   The solid catalyst component is obtained by suspending a magnesium compound (a) in an aromatic hydrocarbon compound (d) to obtain a suspension of a tetravalent titanium halogen compound (b) and an aromatic hydrocarbon compound (d). Then, the resulting solution is contacted with an electron donating compound (c) to obtain a solid product, and the solid product is added with a tetravalent titanium halogen compound (b) and an aromatic hydrocarbon. 2. The catalyst for olefin polymerization according to claim 1, which is prepared by contacting a mixed solution with the compound (d).   After the solid catalyst component is in contact with an alkyl magnesium halide ether solution in contact with a uniform solution of tetraalkoxy titanium, tetraalkoxy silane and an aliphatic hydrocarbon compound, the resulting solid product is contacted with a phthalic acid diester. The solid catalyst component for olefin polymerization according to claim 1, wherein the solid catalyst component is further prepared by contacting with phthalic acid diester and titanium tetrachloride at least once.   The solid catalyst component is contacted with phthalic anhydride in a homogeneous solution obtained by reacting magnesium dihalide, aliphatic hydrocarbon compound and alcohol, then contacted with titanium tetrachloride, and then phthalic acid diester The solid catalyst component for olefin polymerization according to claim 1, wherein the solid catalyst component is prepared by contacting.   2. The olefin polymerization catalyst according to claim 1, wherein the one or more aminosilane compounds are bis (alkylamino) dialkoxysilane or bis (cycloalkylalkylamino) dialkoxysilane.   The one or more aminosilane compounds are bis (t-butylamino) dialkoxysilane, bis (sec-butylamino) dialkoxysilane, bis (iso-butylamino) dialkoxysilane, bis (iso-propylamino) dialkoxy. The olefin polymerization catalyst according to claim 1, which is silane, bis (cyclopentylamino) dialkoxysilane or bis (cyclohexylamino) dialkoxysilane.   The one or more aminosilane compounds are alkyl (alkylamino) dialkoxysilane, cycloalkyl (alkylamino) dialkoxysilane, and decahydronaphthyl (alkylamino) dialkoxysilane. Olefin polymerization catalyst.   The one or more aminosilane compounds are alkyl (t-butylamino) dialkoxysilane, alkyl (iso-propylamino) dialkoxysilane, alkyl (cyclohexylamino) dialkoxysilane, or decahydronaphthyl (alkylamino) dialkoxysilane. The olefin polymerization catalyst according to claim 1, wherein:   The one or more aminosilane compounds are n-propyl (alkylamino) dialkoxysilane, iso-butyl (alkylamino) dialkoxysilane, cyclopentyl (alkylamino) dialkoxysilane, cyclohexyl (alkylamino) dialkoxysilane, or deca The catalyst for olefin polymerization according to claim 1, which is hydronaphthyl (alkylamino) dialkoxysilane. The manufacturing method of the olefin polymer characterized by performing in presence of the catalyst for olefin polymerization of any one of Claims 1-10 . The method for producing an olefin polymer according to claim 11 , wherein the olefin polymer is a propylene polymer.

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